A class of 3-phenyl-2,4(1H,3H)-pyrimidinediones and compositions containing them as active ingredients are useful as herbicides, defoliants and desiccants.
It has been known, that certain 3-phenyl-2,4(1H,3H)-pyrimidinediones are useful in the control of weeds, and they can be prepared by using various processes in the literature; for example WO96/07323, WO96/08151, WO98/41093.
It has also concretely been known in WO98/41093, that the specific 3-phenyl-2,4(1H,3H)-pyrimidinediones can be produced by using the isocyanates and 3-amino or 3-hydrazino-4,4,4-trifluorocrotonate esters.
However, it has not been known therein that they can be produced by using the isocyanates and 3-substituted hydrazino-4,4,4-trifluorocrotonate esters.
The need continues for novel and improved herbicidal, defoliant or desiccant compounds, and compositions containing these compounds, and further for industrial preparation process therefor. This invention relates to novel preparation processes of certain 3-phenyl-2,4(1H,3H)-pyrimidinediones represented by the general formula (I) or their salts, some compounds among them and compositions containing said some compounds for herbicides, defoliants or desiccants, and methods of using these compositions.
This invention relates to a process for producing 3-phenyl-2,4(1H,3H)-pyrimidinediones having the general formula (I) and their salts 
wherein
A1 is hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cyloalkynyl, cycloalkylalkyl, each being optionally substituted,
A2 is hydrogen, xe2x80x94Q1xe2x80x94A3 wherein Q1 is O, S, SO, or SO2; A3 is hydrogen or A4 (A4 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cyloalkynyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, heterocyclicalkyl, each being optionally substituted), xe2x80x94Q1xe2x80x94CQ2xe2x80x94A3 wherein Q2 is O or S, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94CQ2xe2x80x94A3, xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94N(A3)2, xe2x80x94N(Q1xe2x80x94A3)2, xe2x80x94N(CQ2xe2x80x94A3)2, xe2x80x94N(Q1xe2x80x94A3)(CQ2xe2x80x94A3), xe2x80x94N(CQ2xe2x80x94Q2xe2x80x94A3)2, xe2x80x94N(A3)xe2x80x94CQ2xe2x80x94N(A3)2, or xe2x80x94SO2xe2x80x94N(A3)2, each A3 group of (A3)2 being independently same or different, any two of (A1)l and (A2)m groups being optionally combined through a saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N, S, SO, or SO2 linkages to form a cyclic ring having up to 12 membered ring, each being optionally substituted,
l is an integer of 1 to 5, m is an integer of 1 to 3, l+m is an integer of 2 to 5,
R1 is A4, xe2x80x94Q1xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94CQ2xe2x80x94A3, xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94N(A3)2, xe2x80x94N(Q1xe2x80x94A3)2, xe2x80x94N(CQ2xe2x80x94A3)2, xe2x80x94N(Q1xe2x80x94A3)(CQ2xe2x80x94A3), xe2x80x94N(CQ2xe2x80x94Q2xe2x80x94A3)2, xe2x80x94N(A3)xe2x80x94CQ2xe2x80x94N(A3)2, or xe2x80x94SO2xe2x80x94N(A3)2, each A3 group of (A3)2 being independently same or different,
R2 is hydrogen or R1.
R1 and R2 groups being optionally combined together with N of N(R1)(R2) through a saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N, S, SO, or SO2 linkages to form a cyclic ring having up to 12 membered ring, each being optionally substituted,
which comprises reacting the isocyanates represented by the general formula (II) 
wherein A1, A2, l and m are as defined above, and the substituted hydrazono esters represented by the general formula (III) 
wherein R5 is A4, R1 and R2 are as defined above, with or without the presence of a base.
This invention relates to said process for producing 3-phenyl-2,4(1H,3H)-pyrimidinediones having the general formula (I) and their salts.
Some compounds of the formula (I) may form a salt with an acidic substance or a basic substance. The salt with an acidic substance may be an inorganic acid salt such as hydrochloride, hydrobromide, phosphate, sulfate or nitrate. The salt with a basic substance may be a salt of an inorganic or organic base such as sodium salt, potassium salt, calcium salt, quarternary ammonium salt such as ammonium salt or dimethylamine salt.
The substituents concerning the term of xe2x80x9ceach being optionally substitutedxe2x80x9d or xe2x80x9csubstituted or unsubstitutedxe2x80x9d in the various definitions of the formulas (I), (I-a) to (I-c), (II), (II-a) to (II-c), (III), (III-a) to (III-c), may include halogen, cyano, nitro, amino, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, dialkylaminocarbonyl, alkylsulfonylamino, alkoxycarbonylalkoxy, alkylcarbonylamino, alkoxycarbonylamino, bis-acylamino, aminoacyl, aminohalogenoacyl, or aminoalkylsulfonate. Number of the substituents is one or more, when the substituents are two or more, they are same or different.
The term of xe2x80x9calkylxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain, and can include di- and multi-radicals, having number of carbon atoms designated (i.e. C1-6 means one to six carbons). Examples of alkyl groups may include ones with C1-6, preferably C1-4 such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. The term of xe2x80x9calkenylxe2x80x9d, or xe2x80x9calkynylxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain, and can include di- and multi-radicals, having the number of carbon atoms designated (i.e. C2-6 means two to six carbons). Examples of alkenyl or alkynyl groups may include ones with C2-6, preferably C2-4 such as vinyl, propenyl, butenyl, pentenyl, or hexenyl; ethynyl, propynyl, butynyl, pentynyl, or hexynyl. The term of xe2x80x9ccycloalkylxe2x80x9d, xe2x80x9ccycloalkenylxe2x80x9d or xe2x80x9ccycloalkynylxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, cyclic radicals, which may be fully saturated, mono-, or poly-unsaturated, and can include di- and multi-radicals, having the number of carbon atoms designated (i.e. C3-12 means three to twelve carbons). Examples of cycloalkyl, cycloalkenyl or cycloalkynyl group may include ones with C3-12, preferably C3-9, more preferably C3-6 such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; cyclopropenyl, cyclobutenyl, cyclopentenyl, or cyclohexenyl; cyclopropynyl, cyclobutynyl, cyclopentynyl, or cyclohexynyl.
The term of xe2x80x9cacylxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, a group represented by the formula xe2x80x9cxe2x80x94CQ2xe2x80x94A4.
The term of xe2x80x9chalogenxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, fluorine, chlorine, bromine, or iodine. For example, haloalkyl or haloalkoxy group constitutes the alkyl or alkoxy and one or more halogen atoms as mentioned above. When the number of halogen atom is two or more, halogen atoms may be independently same or different.
The substituted hydrazono esters may include the compounds of the formulas (111), (111-1), (111-a) to (111-c) and their isomers; for example, the compounds are represented by the general formula (111) 
and their isomers are represented by the general formula (1111) 
The bases to be used in the processes of the present invention may include inorganic bases such as alkali metals or alkali earth metals, their hydrides, alkoxides, hydroxides or carbonates; metallic sodium, and alkyl lithiums e.g. butyl lithium lithium hydride, sodium hydride, sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate; Grignard Reagents such as (C1-6) alkyl or aryl magnesium halide such as methyl magnesium bromide, ethyl magnesium bromide, n-propyl magnesium bromide, phenyl magnesium bromide, methyl magnesium chloride, dialkyl magnesium, preferably Grignard Reagents, more preferably methyl magnesium bromide; or an organic base such as mono, di, or trialkylamines or alkanolamines (e.g. monomethylamine, dimethylamine, trimethylamine, triethylamine, triethanolamine etc.), pyridine, lutidine, etc.
1) The preferred processes of the invention are as follows.
A process for producing 3-(3-substituted phenyl)-2,4(1H,3H)-pyrimidinediones having the general formula (I-a) and their salts 
wherein
X, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl or thiocarbamoyl, each being optionally substituted,
Z is O, S, SO, SO2 or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, each being optionally substituted,
Ar is a substituted or unsubstituted 3 to 12 membered cyclic ring, it having optionally one or more saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N, S, SO, or SO2 linkages,
R1 is A4, xe2x80x94Q1xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94CQ2xe2x80x94A3, xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94N(A3)2, xe2x80x94N(Q1xe2x80x94A3)2, xe2x80x94N(CQ2xe2x80x94A3)2, xe2x80x94N(Q1xe2x80x94A3)(CQ2xe2x80x94A3), xe2x80x94N(CQ2xe2x80x94Q2xe2x80x94A3)2, xe2x80x94N(A3)xe2x80x94CQ2xe2x80x94N(A3)2 or xe2x80x94SO2xe2x80x94N(A3)2, each A3 group of (A3)2 being independently same or different,
R2 is hydrogen or R1.
R1 and R2 groups being optionally combined together with N of N(R1)(R2) through a saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N, S, SO, or SO2 linkages to form a cyclic ring having up to 12 membered ring, each being optionally substituted, which comprises reacting the isocyanates represented by the general formula (II-a) 
wherein Ar, X, Y, and Z are as defined above, and the substituted hydrazono esters represented by the general formula (III-a) 
wherein R5 is A4, with or without the presence of a base.
2) The more preferred processes of the invention are as follows.
A process for producing 3-(3-substituted phenyl)-2,4(1H,3H)-pyrimidinediones having the general formula (I-b) and their salts 
wherein
X, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl, or thiocarbamoyl, each being optionally substituted,
Z is O, S or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, each being optionally substituted,
Ar is a substituted or unsubstituted aryl or heteroaryl,
R1 is a substituted or unsubstituted protective group,
R2 is hydrogen, alkyl, alkenyl, alkynyl, aryl or protective group, each being optionally substituted,
R1 and R2 groups being optionally combined together with N of N(R1)(R2) through a saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N,S, SO, or SO2 linkages to form a cyclic ring having up to 12 membered ring, each being optionally substituted, which comprises reacting the isocyanates represented by the general formula (II-b) 
wherein Ar, X, Y, and Z are as defined above, and the substituted hydrazono esters represented by the general formula (III-b) 
wherein R5 is A4, with or without the presence of a base.
3) The most preferred processes of the invention are as follows.
A process for producing 3-(3-substituted phenyl)-2,4(1H,3H)-pyrimidinediones having the general formula (I-c) and their salts 
wherein
X, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl or thiocarbamoyl, each being optionally substituted,
Z is O, S, SO, SO2 or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, each being optionally substituted,
Ar is a substituted or unsubstituted 3 to 12 membered cyclic ring, it having optionally one or more saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N, S, SO, or SO2 linkages,
R3 is A4, xe2x80x94Q1xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94CQ2xe2x80x94A3, xe2x80x94CQ2xe2x80x94Q2xe2x80x94A3, xe2x80x94CQ2xe2x80x94N(A3)2, xe2x80x94N(A3)2, xe2x80x94N(Q1xe2x80x94A3)2, xe2x80x94N(CQ2xe2x80x94A3)2, xe2x80x94N(Q1xe2x80x94A3)(CQ2xe2x80x94A3), xe2x80x94N(CQ2xe2x80x94Q2xe2x80x94A3)2, xe2x80x94N(A3)xe2x80x94CQ2xe2x80x94N(A3)2 or xe2x80x94SO2xe2x80x94N(A3)2, each A3 group of (A3)2 being independently same or different,
R4 is hydrogen or R3,
R3 and R4 groups being optionally combined together with C of xe2x95x90C(R3)(R4) through a saturated or unsaturated carbon, xe2x80x94CQ2xe2x80x94, and/or hetero O, N,S, SO, or SO2 linkages to form a cyclic ring having up to 12 membered ring, each being optionally substituted,
which comprises reacting the isocyanates represented by the general formula (II-c) 
and the substituted hydrazono esters represented by the general formula (III-c) 
wherein R5 is A4, with or without the presence of a base.
The term of xe2x80x9carylxe2x80x9d by itself or as part of another substituent, means, unless otherwise stated, aromatic ring in the various definitions of the formulas (I), (I-a) to (I-c), (II), (II-a) to (II-c), (III), (III-a) to (III-c), may include may be a six or twelve membered ring such as phenyl or naphthyl, and the heteroaryl may be five to twelve, or preferably five to six membered ring having at least one hetero atom of nitrogen, oxygen or sulfur, and for example may be pyridyl, pyrimidyl , pyridazinyl, triazolyl, thiazolyl or isothiazolyl, etc.
The protective groups in the definitions of R1 to R4 for the general formulas (I), (I-a) to (I-c), (III), (III-a) to (III-c), may be certain groups provided by conventional reactions for introducing one or more protective groups to an amino group of certain organic compounds using reaction reagents having the protective group. For example, they may include acyl, carbamoyl, sulfonyl or sulfamoyl. Substituents for each of acyl, carbamoyl, sulfonyl or sulfamoyl group, are selected from the group of acceptable substituents as described above: e.g. formyl, acetyl, propionyl, cyclohaxanoyl, propioloyl, crotonyl, acryloyl, methacryloyl, benzoyl, phenylacetyl, anisoyl, toluoxyl (o, m, p), salicyloyl (o, m, p), carbamoyl, dimethylcarbamoyl, oxamoyl, sulfonyl, tosyl (o, m, p), phenylsulfonyl, sulfamoyl, phenylsulfamoyl, etc.
The cyclic ring having up to 12 membered ring in the definitions of R1 to R2 may include a saturated or unsaturated cyclic ring containing the N of N(R1)(R2) in the general formulas (I), (I-a) to (I-b), (III), (III-a) to (II-b) as well as from zero to four hetero atoms selected from the group consisting of O, N, S, SO, or SO2, and the ring optionally substituted by one or more groups of said acceptable substituents: e.g. piperidino, morpholino, terephthalino, 3,4,5,6-tetrahydrophtharino etc. Further, said cyclic ring in the definition of R1 and R2 may also include ones having the general formulas (I-c) and (III-c) ; xe2x80x94Nxe2x95x90C(R3)(R4) wherein R3 and R4 are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or a protective group; or R3 and R4 may combine together with the carbon atom of xe2x95x90C(R3)(R4) to form a substituted or unsubstituted cyclic ring. Such cyclic ring may include a saturated or unsaturated cyclic ring containing from zero to four hetero atoms selected from nitrogen, oxygen and sulfur, and the ring optionally substituted by one or more groups of said acceptable substituents: e.g. methylethylidene, methylpropylidene, benzylidene, phenylbenzylidene, cyclopentylidene, etc.
Among the compounds of the general formula (I), the 3-(3-substituted phenyl)-2,4(1H,3H)-pyrimidinediones of this invention having the general formula (I-c) are novel. 
wherein X, Y, Z, Ar, R3 and R4 are as described above.
The preferred formula (I-c) compounds of this invention are those;
wherein
X, Y are halogen;
Z is oxygen or sulfur;
Ar is pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl, or pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl substituted with up to five substituents independently selected the from group consisting of bromo, chloro, fluoro, iodo, (C1-C4)alkyl, halo(C1-4)alkyl, (C1-4)alkoxy, (C1-4)alkylthio, halo(C1-4)alkoxy, (C1-4)alkylsulfonyl, (C1-C3)alkylsulfinyl, di(C1-4)alkylaminocarbonyl, cyano, nitro, (C1-4)alkylsulfonylamino, (C1-4)alkoxycarbonyl(C1-4)alkoxy, and (C1-4)alkoxycarbonylamino.
The more preferred formula (I-c) compounds of this invention are those;
wherein
X is fluorine;
Y is chlorine;
Z is oxygen or sulfur;
Ar is 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-dimethylaminocarbonyl-2-pyridyl, 3-methylsulfonyl-2-pyridyl, 3-isopropylsulfonyl-2-pyridyl, 6-chloro-3-trifluoromethyl-2-pyridyl, 3,5,6-trifluoropyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimethoxy-2-pyrimidyl, 2,6-dimethoxy-4-pyrimidyl, 4,6-dimethoxy-2-triazinyl, phenyl, 2-iodophenyl, 2-trifluoromethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 4-methylsulfonylaminophenyl, 4-(1-ethoxycarbonylethoxy)phenyl, 2-cyanophenyl, 2-cyano-3-fluorophenyl, 2-cyano-4-fluorophenyl, 2-cyano-4-nitrophenyl, 4-nitro-2-trifluoromethylphenyl, 4-acetylamino-2-trifluoromethylphenyl, 4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolyl, or 5-nitro-2-thiazolyl.
The compounds of this invention having said general formula I can be prepared by the reaction scheme mentioned in Process (1). 
The reaction is carried out by mixing the isocyanates (II) and the hydrazono-esters (III) in the presence of bases, usually by the first step of mixing the compounds III and bases, and then the second step of adding the isocyanates II to thus obtained mixture with or without solvents.
The bases to be used in the processes of the present invention are as described above, and are employed in appropriate methods.
The solvents may include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene; aliphatic hydrocarbons such as pentane, hexane, preferably dimethyl or diethyl ether, tetrahydrofuran, benzene, toluene, pentane and hexane, more preferably tetrahydrofuran.
The additive such as inorganic or organic salts of metal may be used in the process (1). They may include ones of metal atom selected from the group consisting of Mg, Al, B, Zn, Ti and lanthanides (e.g. MgCl2, MgI2, AlCl3, BF3, TiCl4).
The reaction may be conducted usually by using 0.5-2.0 moles of the isocyanates (II) and 0.5-3.0 moles of the bases based on one mole of the compounds (III), preferably 0.7-1.5 moles of the isocyanates (II) and 0.7-2.0 moles of the bases based thereon, and under an inert atmosphere such as nitrogen gas or argon gas.
The reaction is usually conducted at a temperature of xe2x88x92110xc2x0 C. to 150xc2x0 C. and for a period of 1 minute to 5 hours, preferably at a temperature of xe2x88x9278xc2x0 C. to 25xc2x0 C. and for a period of 5 minutes to 1 hour.
The reaction products are subjected to the conventional work-up treatments such as quenching, extracting and drying steps, for example, mixing them with water, extracting with suitable organic solvents and drying to obtain the aimed compounds having said general formula (I).
The intermediates II may be prepared by the methods as described in WO98/41093 or their analogous processes. For example, the intermediates (II-a) can be prepared by the following reaction scheme as mentioned in Process (2). 
Process (2) is carried out by two stages. The first step is carried out by using the reactions of aminophenols (II-1) with aryl halides or heteroaryl halides with or without solvents. The solvents may include acetonitrile, tetrahydroftiran, dimethyl imidazolidine, dimethylsulfoxide, hexamethylphosphoric triamide, N,N-dimethylformamide, acetone, butan-2-one, benzene, toluene or xylene, in the presence of bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium t-butoxide, potassium fluoride, or sodium hydride. Catalysts may or may not be used. Such catalysts include copper(1)chloride, copper(1)oxide, copper, copper(1)alkoxides, alkyl cuprates, palladium(0), tetrabutylammonium halides, or 8-quinolinol. The reaction temperature is usually from 0xc2x0 C. to 250xc2x0 C., preferably from 20xc2x0 C. to 120xc2x0 C. The reaction time is from 1 to 12 hours, preferably from 2 to 6 hours.
The diaryl ethers (II-2) may also be prepared by treatment of aminophenols (II-1) with aryl-lead tricarboxylates, triphenylbismuth-diacetate, triphenylbismuth-trifluoroacetate or diphenyliodonium halides in the presence of solvents such as benzene, toluene, dichloromethane, dichloroethane, chloroform or water, with or without catalysts such as copper, or transition metals.
The reaction may be conducted usually by using 0.1-10 moles of the Ar-Hal based on the aminophenol. The temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, and the reaction time from 10 minutes to 72 hours. The temperature is preferably from 20xc2x0 C. to the reflux temperature of the mixture, and the time preferably 2 to 6 hours.
The second step requires treatment of the amines (II-2) with phosgene or triphosgene in solvents such as hexane, heptane, benzene, toluene, xylene, or ethyl acetate. The reaction temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, preferably at the reflux temperature thereof. The reaction time is usually from 30 minutes to 6 hours, preferably from 2 to 3 hours.
The other intermediates (III) can be prepared by the methods mentioned in Process (3). 
wherein R5 is as described above, T is halogen, ether or ester forming residue (e.g. acyloxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, sulfonyloxy).
Process (3) is also usually carried out by two steps.
The first step is carried out by using the reactions of alkali metal (e.g. lithium, sodium, potassium) esters of 4,4,4-trifluoroacetoacetate (III-1) with a halogenating agent such as phosphorus oxychloride, phosphorus pentachloride, thionyl chloride, etc., and reagents for elimination reactions such as triflic acid, its halide, anhydride or ester with or without solvents. The reaction may be conducted usually by using 0.3-3.0 moles of the reagents thereof based on one mole of the alkali metal esters of 4,4,4-trifluoroacetoacetate (III-1). The solvents may include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dioxane, tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, or N,N-dimethylformamide, dimethylsulfoxide, preferably dimethyl or diethyl ether. The reaction temperature is usually from xe2x88x9220xc2x0 C. to 100xc2x0 C., preferably from xe2x88x9210xc2x0 C. to 25xc2x0 C. The reaction time is from 0.1 to 12 hours, preferably from 0.5 to 2 hours.
The second step is carried out by using the reaction of 2-butenoic acid, 4,4,4-trifluoro-3-O-substituted, esters (III-2) and substituted hydrazines with or without solvents and bases. Examples of substituted hydrazines may include ones prepared by reactions of hydrazine with ketones having R1xe2x80x94COxe2x80x94R2 (wherein R1 and R2 are as defined above.) (See. Day, A. C., Whiting, M. C. Organic Syntheses, Coll. Vol. VI, 10.), or by reactions of hydrazine with reaction reagents for conventional reactions for introducing one or more radicals including protective groups to an amino group of certain organic compounds.
The reaction proceeds without any solvents, but is normally accelerated by employing solvents.
Further reaction requires solvents such as aliphatic hydrocarbons e,g, hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as chloroform and methylene chloride, and the bases of inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, or sodium hydride, or organic amines such as pyridine, triethylamine, diisopropylethylamine, DBU, DBN.
The reaction may be conducted usually by using 0.3-5 moles of the substituted hydrazines based on one mole of the 2-butenoic acid, 4,4,4-trifluoro-3-[[(trifluoromethyl)sulfonyl]oxy]-, esters (III-2).
The reaction temperature is usually from xe2x88x9230xc2x0 C. to 150xc2x0 C., preferably from 0xc2x0 C. to 75xc2x0 C. The reaction time requires normally from 30 minutes to 20 hours, preferably from 60 minutes to 12 hours.
The intermediates (III) can be also prepared sometimes directly by the methods mentioned below. 
The process is also carried out under the same or analogous conditions as described in Process (3).
Further the compounds of the general formulas (I), (I-a), and (I-b) can be optionally applied to the reactions for changing the group; xe2x80x94N(R1)(R2) in the chemical structure of the general formulas (I), (I-a), and (I-b) to the amino group; xe2x80x94NH2. Preferably, the compounds having xe2x80x94Nxe2x95x90C(R3)(R4) group in the general formula (I-c) can be changed into the compounds having the amino group; xe2x80x94NH2 For example, the reaction is carried out by reacting compounds of the general formulas (I), and (I-a) to (I-c) with an aqueous solution of mineral acid such as hydrochloric acid in the presence of alcohol such as methanol at a temperature of from 0xc2x0 C. to 150xc2x0 C., usually under a reflux condition. The compounds obtained are also useful as herbicides, defoliants or desiccants, particularly herbicides for controlling undesired weeds in crop land.
The examples according to the present invention will now be illustrated as follows.